Intramolecular sulphur(IV)-oxygen interaction in sulphoxides and sulphilimines with 2-methoxycarbonyl-phenyl and 2-nitrophenyl groups: an X-ray study

Á Kucsman, I. Kapovits, I. Kövesdi, A. Kálmán, L. Párkányí

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Abstract

The molecular structures of methyl 2-(methylsulphinyl)benzoate, S-(2-methoxy-carbonylphenyl)-S-methyl-N-(4-methoxyphenylsulphonyl)- sulphilimine, dimethyl 2,2′-sulphinyldibenzoate, methyl 2-(2-nitrophenylsulphinyl) benzoate, 2,2′-dinitrodiphenyl sulphoxide and methyl 2-(2-nitrophenylsulphinyl)phenylacetate exhibiting S(IV)⋯O-(carbonyl) or S(IV)⋯O(nitro) close contact have been investigated by X-ray diffraction. The observed axial (ArMeSO, ArMeSNSO2Ar) and axial-twist (Ar2SO) conformations are interpreted by taking into account steric effects, conjugation and sulphur(IV)-oxygen interaction. Linear and non-linear X=S(IV)⋯O close contacts (2.664-2.778 and 2.847-3.618 A, respectively) related to favourable "bond direction" and unfavourable "lonepair direction" approaches are discussed and compared with corresponding (shorter) XS(II)⋯O close contacts. The relative positions of aryl rings, the geometry of rings with S⋯O contacts and the nature of the counter-atom (X = O, N) mainly determine sulphur(IV)-oxygen interaction. The data are in good agreement with the nearly equal anchimeric assistance of the o-CO2Me and o-CO2H groups, and with the lack of neighbouring-group activity in cases where six-membered rings with S⋯O contacts should be formed. Sulphur-oxygen bond lengths in OS⋯O and OSO systems with close contacts or hypervalent bonds are compared. Changes in CO, NO and S(IV)Car bond lengths caused by sulphur(IV)-oxygen interaction are negligible.

Original languageEnglish
Pages (from-to)135-148
Number of pages14
JournalJournal of Molecular Structure
Volume127
Issue number1-2
DOIs
Publication statusPublished - 1985

Fingerprint

Sulfur
sulfur
OSO
X-Rays
Oxygen
X rays
Benzoates
Bond length
oxygen
rings
x rays
interactions
Carbon Monoxide
Molecular Structure
conjugation
X-Ray Diffraction
Molecular structure
Conformations
counters
molecular structure

ASJC Scopus subject areas

  • Structural Biology
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Materials Science (miscellaneous)
  • Atomic and Molecular Physics, and Optics

Cite this

@article{c713621f7bc4415491467163cbbcb04e,
title = "Intramolecular sulphur(IV)-oxygen interaction in sulphoxides and sulphilimines with 2-methoxycarbonyl-phenyl and 2-nitrophenyl groups: an X-ray study",
abstract = "The molecular structures of methyl 2-(methylsulphinyl)benzoate, S-(2-methoxy-carbonylphenyl)-S-methyl-N-(4-methoxyphenylsulphonyl)- sulphilimine, dimethyl 2,2′-sulphinyldibenzoate, methyl 2-(2-nitrophenylsulphinyl) benzoate, 2,2′-dinitrodiphenyl sulphoxide and methyl 2-(2-nitrophenylsulphinyl)phenylacetate exhibiting S(IV)⋯O-(carbonyl) or S(IV)⋯O(nitro) close contact have been investigated by X-ray diffraction. The observed axial (ArMeSO, ArMeSNSO2Ar) and axial-twist (Ar2SO) conformations are interpreted by taking into account steric effects, conjugation and sulphur(IV)-oxygen interaction. Linear and non-linear X=S(IV)⋯O close contacts (2.664-2.778 and 2.847-3.618 A, respectively) related to favourable {"}bond direction{"} and unfavourable {"}lonepair direction{"} approaches are discussed and compared with corresponding (shorter) XS(II)⋯O close contacts. The relative positions of aryl rings, the geometry of rings with S⋯O contacts and the nature of the counter-atom (X = O, N) mainly determine sulphur(IV)-oxygen interaction. The data are in good agreement with the nearly equal anchimeric assistance of the o-CO2Me and o-CO2H groups, and with the lack of neighbouring-group activity in cases where six-membered rings with S⋯O contacts should be formed. Sulphur-oxygen bond lengths in OS⋯O and OSO systems with close contacts or hypervalent bonds are compared. Changes in CO, NO and S(IV)Car bond lengths caused by sulphur(IV)-oxygen interaction are negligible.",
author = "{\'A} Kucsman and I. Kapovits and I. K{\"o}vesdi and A. K{\'a}lm{\'a}n and L. P{\'a}rk{\'a}ny{\'i}",
year = "1985",
doi = "10.1016/0022-2860(85)80158-7",
language = "English",
volume = "127",
pages = "135--148",
journal = "Journal of Molecular Structure",
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TY - JOUR

T1 - Intramolecular sulphur(IV)-oxygen interaction in sulphoxides and sulphilimines with 2-methoxycarbonyl-phenyl and 2-nitrophenyl groups

T2 - an X-ray study

AU - Kucsman, Á

AU - Kapovits, I.

AU - Kövesdi, I.

AU - Kálmán, A.

AU - Párkányí, L.

PY - 1985

Y1 - 1985

N2 - The molecular structures of methyl 2-(methylsulphinyl)benzoate, S-(2-methoxy-carbonylphenyl)-S-methyl-N-(4-methoxyphenylsulphonyl)- sulphilimine, dimethyl 2,2′-sulphinyldibenzoate, methyl 2-(2-nitrophenylsulphinyl) benzoate, 2,2′-dinitrodiphenyl sulphoxide and methyl 2-(2-nitrophenylsulphinyl)phenylacetate exhibiting S(IV)⋯O-(carbonyl) or S(IV)⋯O(nitro) close contact have been investigated by X-ray diffraction. The observed axial (ArMeSO, ArMeSNSO2Ar) and axial-twist (Ar2SO) conformations are interpreted by taking into account steric effects, conjugation and sulphur(IV)-oxygen interaction. Linear and non-linear X=S(IV)⋯O close contacts (2.664-2.778 and 2.847-3.618 A, respectively) related to favourable "bond direction" and unfavourable "lonepair direction" approaches are discussed and compared with corresponding (shorter) XS(II)⋯O close contacts. The relative positions of aryl rings, the geometry of rings with S⋯O contacts and the nature of the counter-atom (X = O, N) mainly determine sulphur(IV)-oxygen interaction. The data are in good agreement with the nearly equal anchimeric assistance of the o-CO2Me and o-CO2H groups, and with the lack of neighbouring-group activity in cases where six-membered rings with S⋯O contacts should be formed. Sulphur-oxygen bond lengths in OS⋯O and OSO systems with close contacts or hypervalent bonds are compared. Changes in CO, NO and S(IV)Car bond lengths caused by sulphur(IV)-oxygen interaction are negligible.

AB - The molecular structures of methyl 2-(methylsulphinyl)benzoate, S-(2-methoxy-carbonylphenyl)-S-methyl-N-(4-methoxyphenylsulphonyl)- sulphilimine, dimethyl 2,2′-sulphinyldibenzoate, methyl 2-(2-nitrophenylsulphinyl) benzoate, 2,2′-dinitrodiphenyl sulphoxide and methyl 2-(2-nitrophenylsulphinyl)phenylacetate exhibiting S(IV)⋯O-(carbonyl) or S(IV)⋯O(nitro) close contact have been investigated by X-ray diffraction. The observed axial (ArMeSO, ArMeSNSO2Ar) and axial-twist (Ar2SO) conformations are interpreted by taking into account steric effects, conjugation and sulphur(IV)-oxygen interaction. Linear and non-linear X=S(IV)⋯O close contacts (2.664-2.778 and 2.847-3.618 A, respectively) related to favourable "bond direction" and unfavourable "lonepair direction" approaches are discussed and compared with corresponding (shorter) XS(II)⋯O close contacts. The relative positions of aryl rings, the geometry of rings with S⋯O contacts and the nature of the counter-atom (X = O, N) mainly determine sulphur(IV)-oxygen interaction. The data are in good agreement with the nearly equal anchimeric assistance of the o-CO2Me and o-CO2H groups, and with the lack of neighbouring-group activity in cases where six-membered rings with S⋯O contacts should be formed. Sulphur-oxygen bond lengths in OS⋯O and OSO systems with close contacts or hypervalent bonds are compared. Changes in CO, NO and S(IV)Car bond lengths caused by sulphur(IV)-oxygen interaction are negligible.

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U2 - 10.1016/0022-2860(85)80158-7

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